US5852197A - Cyclic disphosphoric esters, a process for their preparation and their use - Google Patents
Cyclic disphosphoric esters, a process for their preparation and their use Download PDFInfo
- Publication number
- US5852197A US5852197A US08/680,133 US68013396A US5852197A US 5852197 A US5852197 A US 5852197A US 68013396 A US68013396 A US 68013396A US 5852197 A US5852197 A US 5852197A
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- US
- United States
- Prior art keywords
- cyclic
- esters
- disphosphoric
- preparation
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 150000002148 esters Chemical class 0.000 title claims abstract description 13
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 11
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims abstract description 3
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims abstract description 3
- 101150108015 STR6 gene Proteins 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 2
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BGGGMYCMZTXZBY-UHFFFAOYSA-N (3-hydroxyphenyl) phosphono hydrogen phosphate Chemical compound OC1=CC=CC(OP(O)(=O)OP(O)(O)=O)=C1 BGGGMYCMZTXZBY-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
Definitions
- JP-A 54 080 355 describes a cyclic disphosphoric ester of the formula ##STR2## in which the phosphorus-containing groups are bound in the 1,4 position to the benzene molecule.
- the invention likewise relates to a process for preparing the abovementioned cyclic diphosphoric esters, in which, in a 1st reaction step, diols are reacted with phosphorus oxychloride to give the tetrachloride of the diphosphoric ester: ##STR4##
- the reactions can be carried out in suitable inert solvents, such as aromatics, aliphatics, cycloaliphatics or chloroaliphatics, and in the presence of suitable tertiary amines, such as triethylamine or pyridine, and in the presence of suitable catalysts, such as aluminum chloride.
- suitable inert solvents such as aromatics, aliphatics, cycloaliphatics or chloroaliphatics
- suitable tertiary amines such as triethylamine or pyridine
- suitable catalysts such as aluminum chloride.
- the reactions can be carried out at atmospheric pressure or under reduced pressure.
- the invention further relates to the use of the cyclic diphosphoric esters of the invention as flame retardants.
- a first reaction step 110 g of 1,3-dihydroxybenzene (resorcinol) were reacted with 461 g of phosphorus oxychloride in accordance with DE-OS 22 00 137, Example 8 ! to give the tetrachloride of the resorcinol diphosphate.
- the crude product obtained was purified by vacuum distillation.
- the product is 1,3-bis 2-oxo-5,5-dimethyl-1,3,2-dioxaphos-phorinanyl-2-oxy!benzene.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to cyclic diphosphoric esters of the formula ##STR1## with R=methylethylene, 1,3-cyclohexylene, 1,4-cyclo-hexylene or 1,3-phenylene, a process for their preparation and their use as flame retardants.
Description
Some cyclic diphosphoric esters are known from the prior art. Thus, JP-A 54 080 355 describes a cyclic disphosphoric ester of the formula ##STR2## in which the phosphorus-containing groups are bound in the 1,4 position to the benzene molecule.
Surprisingly, a series of novel cyclic diphosphoric esters have now been able to be synthesized and analytically characterized.
The present invention therefore relates to novel cyclic diphosphoric esters of the formula ##STR3## with R=methylethylene, 1,3-cyclohexylene, 1,4-cyclo-hexylene or 1,3-phenylene.
The invention likewise relates to a process for preparing the abovementioned cyclic diphosphoric esters, in which, in a 1st reaction step, diols are reacted with phosphorus oxychloride to give the tetrachloride of the diphosphoric ester: ##STR4##
The tetrachloride (I) is then reacted with 2,2-dimethyl-1,3-propanediol in a 2nd reaction step at elevated temperature, the cyclic diphosphoric ester (II) being formed with elimination of hydrogen chloride: ##STR5##
The reactions can be carried out in suitable inert solvents, such as aromatics, aliphatics, cycloaliphatics or chloroaliphatics, and in the presence of suitable tertiary amines, such as triethylamine or pyridine, and in the presence of suitable catalysts, such as aluminum chloride.
The reactions can be carried out at atmospheric pressure or under reduced pressure.
The invention further relates to the use of the cyclic diphosphoric esters of the invention as flame retardants.
In a first reaction step, 110 g of 1,3-dihydroxybenzene (resorcinol) were reacted with 461 g of phosphorus oxychloride in accordance with DE-OS 22 00 137, Example 8 ! to give the tetrachloride of the resorcinol diphosphate. The crude product obtained was purified by vacuum distillation.
For the next reaction step, 172 g (1 mol) of this product were then dissolved in 500 ml of xylene in a stirred reactor, 104 g (1 mol) of 2,2-dimethyl-1,3-propanediol and 1.5 g of aluminum chloride (anhydrous) were added and brought to reaction in the course of 5 hours with stirring in the temperature range of 20°-120° C. After cooling to room temperature, the coarsely crystalline solids were filtered off, washed with toluene and then recrystallized from ethanol/water. 184 g of a colorless, crystalline product having the melting point 161°-163° C. were obtained, the elemental analysis of which gave the following values:
Carbon: 46.6% (theoretical for C16 H24 O8 P2 : 47.3%)
Hydrogen: 6.0% (theoretical for C16 H24 O8 P2 : 6.0%)
Phosphorus: 15.2% (theoretical for C16 H24 O8 P2 : 15.2%)
According to the above analytical values and the 1 H-NMR analysis (FIG. 1) and the 31 P-NMR analysis (FIG. 2), the product is 1,3-bis 2-oxo-5,5-dimethyl-1,3,2-dioxaphos-phorinanyl-2-oxy!benzene.
Claims (2)
1. A cyclic diphosphoric ester of the formula ##STR6## with R=1,3-phenylene.
2. A cyclic disphosphoric ester of the formula ##STR7## with R=1,3-cyclohexylene or 1,4-cyclohexylene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19525950A DE19525950A1 (en) | 1995-07-17 | 1995-07-17 | Cyclic diphosphoric acid esters and process for their preparation |
| DE19525950.5 | 1995-07-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5852197A true US5852197A (en) | 1998-12-22 |
Family
ID=7767004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/680,133 Expired - Fee Related US5852197A (en) | 1995-07-17 | 1996-07-15 | Cyclic disphosphoric esters, a process for their preparation and their use |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5852197A (en) |
| EP (1) | EP0754697A1 (en) |
| JP (1) | JPH0931086A (en) |
| DE (1) | DE19525950A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6734239B1 (en) | 1999-07-09 | 2004-05-11 | Daihachi Chemical Industry Co., Ltd. | Flame retardants for resins and flame-retarded resin compositions containing the same |
| CN115304741A (en) * | 2022-08-30 | 2022-11-08 | 上海嘉均瑞科技有限公司 | Polyurethane anti-seepage sealing ring and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE961354C (en) * | 1953-04-02 | 1957-04-04 | Union Carbide & Carbon Corp | Process for the preparation of 2-oxo-1, 3, 2-dioxaphospholanes and 2-oxo-1, 3, 2-dioxaphosphorinanes |
| US2859086A (en) * | 1954-09-27 | 1958-11-04 | Union Carbide Corp | Process utilizing phosphorinanyl derivatives for dyeing articles made from acrylonitrile-containing polymers |
| US2952701A (en) * | 1957-04-15 | 1960-09-13 | Eastman Kodak Co | Organophosphorus derivatives of 2, 2-dimethyl-1, 3-propanediol |
| US3965220A (en) * | 1971-06-24 | 1976-06-22 | Monsanto Company | Preparation of esters of phosphorus acids |
| US3970635A (en) * | 1974-01-28 | 1976-07-20 | Monsanto Company | Fire retardant polyester fibers |
| JPS5480355A (en) * | 1977-12-08 | 1979-06-27 | Mitsubishi Rayon Co Ltd | Flame-retardant polyester composition |
| WO1980001697A1 (en) * | 1979-02-14 | 1980-08-21 | Sandoz Ag | Fire proof material based on organic polymers |
| US4458431A (en) * | 1982-04-05 | 1984-07-10 | Sinclair Suzanne E | Boot for pet animal |
| EP0617042A1 (en) * | 1993-03-16 | 1994-09-28 | Daihachi Chemical Industry Co., Ltd. | Organic phosphorus compounds and flame-retarded resin compositions containing the same |
-
1995
- 1995-07-17 DE DE19525950A patent/DE19525950A1/en not_active Withdrawn
-
1996
- 1996-06-22 EP EP96110100A patent/EP0754697A1/en not_active Withdrawn
- 1996-07-15 US US08/680,133 patent/US5852197A/en not_active Expired - Fee Related
- 1996-07-16 JP JP8186376A patent/JPH0931086A/en not_active Withdrawn
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE961354C (en) * | 1953-04-02 | 1957-04-04 | Union Carbide & Carbon Corp | Process for the preparation of 2-oxo-1, 3, 2-dioxaphospholanes and 2-oxo-1, 3, 2-dioxaphosphorinanes |
| US2974158A (en) * | 1953-04-02 | 1961-03-07 | Union Carbide Corp | Preparation of bi-heterocyclic phosphorus containing compounds |
| US2859086A (en) * | 1954-09-27 | 1958-11-04 | Union Carbide Corp | Process utilizing phosphorinanyl derivatives for dyeing articles made from acrylonitrile-containing polymers |
| US2952701A (en) * | 1957-04-15 | 1960-09-13 | Eastman Kodak Co | Organophosphorus derivatives of 2, 2-dimethyl-1, 3-propanediol |
| US3965220A (en) * | 1971-06-24 | 1976-06-22 | Monsanto Company | Preparation of esters of phosphorus acids |
| US3970635A (en) * | 1974-01-28 | 1976-07-20 | Monsanto Company | Fire retardant polyester fibers |
| JPS5480355A (en) * | 1977-12-08 | 1979-06-27 | Mitsubishi Rayon Co Ltd | Flame-retardant polyester composition |
| WO1980001697A1 (en) * | 1979-02-14 | 1980-08-21 | Sandoz Ag | Fire proof material based on organic polymers |
| US4388431A (en) * | 1979-02-14 | 1983-06-14 | Sandoz Ltd. | Flameproofed organic materials |
| US4458431A (en) * | 1982-04-05 | 1984-07-10 | Sinclair Suzanne E | Boot for pet animal |
| EP0617042A1 (en) * | 1993-03-16 | 1994-09-28 | Daihachi Chemical Industry Co., Ltd. | Organic phosphorus compounds and flame-retarded resin compositions containing the same |
| US5401788A (en) * | 1993-03-16 | 1995-03-28 | Daihachi Chemical Industry Co., Ltd. | Organic phosphorus compounds and flame-retarded resin compositions containing the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6734239B1 (en) | 1999-07-09 | 2004-05-11 | Daihachi Chemical Industry Co., Ltd. | Flame retardants for resins and flame-retarded resin compositions containing the same |
| CN115304741A (en) * | 2022-08-30 | 2022-11-08 | 上海嘉均瑞科技有限公司 | Polyurethane anti-seepage sealing ring and preparation method thereof |
| CN115304741B (en) * | 2022-08-30 | 2023-09-01 | 兴宇汽车零部件股份有限公司 | Polyurethane anti-seepage sealing ring and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0754697A1 (en) | 1997-01-22 |
| JPH0931086A (en) | 1997-02-04 |
| DE19525950A1 (en) | 1997-01-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: HOECHST AKTIENGESELLSCHAFT, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:STAENDEKE, HORST;REEL/FRAME:008105/0837 Effective date: 19960618 |
|
| AS | Assignment |
Owner name: CLARIANT GMBH, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HOECHST AKTIENGESELLSCHAFT;REEL/FRAME:009558/0062 Effective date: 19980917 |
|
| REMI | Maintenance fee reminder mailed | ||
| LAPS | Lapse for failure to pay maintenance fees | ||
| LAPS | Lapse for failure to pay maintenance fees |
Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20021222 |